CN103966889A - Compound and preparation method thereof, and pulp and paper using compound - Google Patents
Compound and preparation method thereof, and pulp and paper using compound Download PDFInfo
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- CN103966889A CN103966889A CN201310045150.XA CN201310045150A CN103966889A CN 103966889 A CN103966889 A CN 103966889A CN 201310045150 A CN201310045150 A CN 201310045150A CN 103966889 A CN103966889 A CN 103966889A
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- fibrillation
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
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Abstract
The invention provides a microfibrillated cellulose-filling material compound applied to the field of papermaking. The microfibrillated cellulose-filling material compound is mainly prepared from a microfibrillated cellulose material, a filling material and latex through compounding, wherein in the compound, the oven dry mass of the microfibrillated cellulose material accounts for 0.1 to 10% of the mass of the filling material, the mass of the latex accounts for 0.1 to 15% of the mass of the filling material, and the glass transition temperature of the latex is less than 20 DEG C. The invention further provides a preparation method for the compound and pulp and paper prepared by using the compound. Through addition of the compound into the pulp, loss of the filling material can be effectively reduced, and the paper prepared from the pulp through paper making has a high ash retention rate.
Description
Technical field
The present invention relates to fibrillation fiber-filler compound of a kind of field of papermaking use and preparation method thereof, and apply slurry and the paper that this fibrillation fiber-filler compound makes.
Background technology
The fibrillation cellulose that adopts Mechanical Method, TEMPO catalytic oxidation to prepare comprises water-soluble and water-insoluble cellulose, its fiber size length between 100 nanometers to several millimeters, width between 3-4 nanometer to tens micron.Because a large amount of carboxyls is contained on surface, and water retention value is high, and specific area is large, so fibrillation fiber prepared by TEMPO catalytic oxidation is usually added in paper making pulp to improve the performances such as intensity of paper.
At present, the method reducing costs in paper industry is to use the mineral filler of relative low price.But, add paper after filler due to the existence of mineral filler particles, hindered and between fibrillation cellulose, formed chemically stable Hydrogenbond; Meanwhile, mineral filler, due to its lacking toughness, has also hindered combination degree between fibrillation cellulose.In addition, fibrillation cellulose surface is containing negative electrical charge, stronger to carrying equally the electrostatic repulsion of negative point or nearly neutral filler, and filler particles is more tiny, and agglomeration more likely occurs.Therefore,, if add fibrillation cellulose and filler in paper making pulp simultaneously, filler distributes very inhomogeneous at fibrillation fiber surface, affect the lifting of filler retention.
Summary of the invention
In view of this, be necessary to provide a kind of fibrillation fiber-filler compound effectively addressing the above problem and preparation method thereof.
In addition, be also necessary to provide a kind of slurry of applying above-mentioned fibrillation fiber-filler compound.
In addition, be also necessary to provide a kind of paper that above-mentioned slurry makes of applying.
A kind of fibrillation fiber-filler compound, it is mainly composited by fibrillation fibrous material, filler and latex, the 0.1%-10% that wherein in this compound, fibrillation fibrous material over dry quality is packing quality, latex quality is the 0.1%-15% of packing quality, and this latex is the latex that vitrification point is less than 20 ℃.
A preparation method for fibrillation fiber-filler compound, mixes the latex of the 0.1%-15% of the fibrillation cellulose of the 0.1%-20% of filler, packing quality and packing quality to make, and this latex is the latex that vitrification point is less than 20 ℃.
A kind of slurry, it contains fibrillation fiber-filler compound, this compound is mainly composited by fibrillation fibrous material, filler and latex, the 0.1%-10% that in this compound, fibrillation fibrous material over dry quality is packing quality, latex quality is the 0.1%-15% of packing quality, and this latex is the latex that vitrification point is less than 20 ℃.
Apply the paper that above-mentioned slurry is manufactured paper with pulp and made, in this paper, contain fibrillation fibrous material, filler, latex.
Fibrillation fiber-filler compound of the present invention, by introducing latex that vitrification point is lower as the bonding agent between fibrillation fiber and filler, makes filler can be attached to equably fibrillation fiber surface.This fibrillation fiber-filler compound is made an addition in slurry, can effectively reduce the loss of filler, the paper that slurry is manufactured paper with pulp make has higher ash content retention rate.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (multiplication factor: 1500) of the fibrillation fiber-filler compound of a preferred embodiment of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph (multiplication factor: 1500) of the fibrillation fiber-filler compound (not containing bonding agent) of comparative example of the present invention.
The specific embodiment
The fibrillation fibrous material that the present invention uses adopts known TEMPO catalytic oxidation preparation, is specially: fibrous raw material is through take the oxidation reaction that TEMPO is catalyst, then carries out mechanical treatment acquisition.
The invention provides and use TEMPO to prepare the cellulosic method example of fibrillation for catalyst, specifically comprise the steps:
(a) get (chemical bleaching slurry) processing of pulling an oar of BKP slurry.
(b) get the chemical bleaching slurry of 100 parts by mass, adjust slurry dense to <2%.
(c) in the chemical bleaching slurry after dilution, add TEMPO(2,2,6,6-tetramethyl-1-piperidines-N-oxygen radical and derivative thereof), the amount adding is 0.001-1 parts by mass.
(d) add 0.01-10 parts by mass cocatalyst, cocatalyst comprises halide and (or) borate compound, and described halide is one or both or its mixture of bromide, iodide.
(e) add 0.1-20 mass parts of oxidant (clorox), initiation reaction.The pH that controls reaction solution system in course of reaction is 9.5-11.Oxidant is by the locational alcohol of the C6 in cellulosic molecule (hydroxyl), height selective oxidation is carboxyl, carboxyl has the elecrtonegativity stronger with respect to hydroxyl, make the layer structure in fiber molecule that Coulomb repulsion more easily occur, can be relatively easy to occur fibrillation effect, generate water-soluble and non-water-soluble cellulose and the derivative of fibrillation.
(f) reaction, after 0.5-4 hour, obtains a kind of mixture, contains oxidized fibre, TEMPO, cocatalyst and water;
(g) mixture can further partly or entirely be removed cocatalyst and unnecessary salinity by desalter;
(h) mixture can further pass through mechanical treatment, as high pressure homogenization device, ultrasonic wave processing mode fibrillation gained mixture.
Gained fibrillation cellulosic material surface carboxyl-content is 0.06-1.7mmol/g, and described fibrous material surface carboxyl may comprise the cellulose alkali metal salt of carboxyl, cellulosic carboxylic acid DDGS or soluble thing.Fibrillation fibrous material (MFC) complicated prepared by TEMPO catalytic oxidation, contain water-soluble and water-insoluble cellulose, water miscible cellulose includes nano micro crystal cellulose (NCC), nanometer fibrillation cellulose (NFC), compound sugar, fibrillation cellulose and derivative thereof; On water-insoluble cellulosic fiber finer cell wall, may contain water miscible cellulose (as NFC).The fibrillation fibrous material of TEMPO catalytic oxidation preparation preparation, has strong negative electrical charge, and fiber surface is evenly distributed with carboxyl.Meanwhile, filler particles is easily obtained good dispersion in the aqueous slurry of fibrillation fibrous material.But due to the complexity of fibrillation fibrous material, its fibre length may be between the scope that is less than 1 micron-several millimeters, and the original fiber degree of fiber is not identical, the fibre bundle surface that original fiber degree is higher easily deposits more filler particles.
Fibrillation fiber-filler compound, its main stuffing, fibrillation fibrous material and bonding agent are composited.The 0.1%-10% that wherein fibrillation fibrous material over dry quality is packing quality, the 0.1%-15% that bonding agent quality is packing quality.In this fibrillation fiber-filler compound, also contain water.
Fibrillation fibrous material prepared by the employing TEMPO catalytic oxidation that the present invention uses, has following feature: (1) strong negative electrical charge, and its surperficial carboxyl-content reaches 0.06-1.7mmol/g; (2) in fibrillation fiber over dry quality, the quality percentage composition of water-soluble cellulose is 0.1%-50%, and the cellulosic quality percentage composition of water-insoluble is 10%-99.9%.
This filler is conventional filler, as grinding calcium carbonate, winnofil, kaolin, talcum powder, titanium dioxide can, electronegativity does not require yet, particle diameter preferably 50% is less than or equal to 2 microns with the packing material size of improving quality.
This bonding agent is the lower latex of vitrification point (Tg), the latex that Tg is less than 20 ℃, and more preferably Tg is less than or equal to 10 ℃.Described latex is optional from polybutadiene latex, styrene-butadiene latex, carboxylic styrene butadiene latex, one or more of CATION styrene-butadiene latex, polyvinyl acetate Ruzhong.Described latex exists with aqueous dispersions form.Because reaction system is higher than vitrification point, filler grain can be at aqueous slurry surface deposition filler grain.
The interpolation of latex makes filler particles can be distributed in more uniformly fibrillation fibrous material surface, and a kind of possible mechanism is as follows: under the vitrification point condition higher than latex, first latex becomes more unstable, and breakdown of emulsion occurs; The specific area of filler is larger, more easily adsorbs the latex macromolecular chain after breakdown of emulsion; Therefore the carbon-carbon double bond in latex composition is contained on the surface of filler; Carbon-carbon double bond thereby unstable, further with fibrillation fibrous material in water-soluble cellulose have an effect (as cellulose carboxylic acid and sodium salt).So, latex is equivalent to medium, the bonding agent between fibrillation fibrous material and filler, makes filler can be attached to equably fibrillation fibrous material surface.
The preparation of this fibrillation fiber-filler compound can be mixed directly the bonding agent (latex) of the fibrillation cellulose of the 0.1%-10% of filler, packing quality, packing quality 0.1%-15%, for not restriction of order of addition, the temperature of controlling mixed liquor in preparation process is 20-110 ℃, preferably 20-70 ℃, is more preferably 30-50 ℃.
The preferred preparation method who the invention provides this fibrillation fiber-filler compound, it comprises the steps: to provide filler; The fibrillation fibrous material that adds relative packing quality 0.1%-10%, continues to add the latex of relative packing quality 0.1%-15%, and under 20-110 ℃ of condition, 800 revs/min (RPM) is lower to be stirred 5 minutes.
Preferably, in this fibrillation fiber-filler compound preparation process, also alternative is added crosslinking agent.This crosslinking agent specifically can be borate, borax, twain-aldehyde compound crosslinking agent, and its addition is the 0.1%-15% of bonding agent quality.The effect of this crosslinking agent is to cause the crosslinked of latex and fibrillation fibrous material (water-soluble or water-insoluble), and the network structure being cross-linked to form is conducive to filler keeping on fibrillation fibrous material surface more.The big or small uniformity that covers the filler particles on fibrillation fibrous material surface in this compound is less than 10.Note: the account form of surface evenness: choose in SEM sample and specify area by ImageJ software, be converted into after 8 figure place images, by calculating pixel gray value, calculate the pixel value of filler particle size.The uniformity here refers to, and the standard deviation Standard Deviation of granular size is divided by the mean value Mean of granular size.
A preparation method for the slurry that contains above-mentioned fibrillation fiber-filler compound, it comprises the steps:
(1) provide a kind of slurry, slurry kind is not limit.
(2) provide above-mentioned fibrillation fiber-filler compound.
(3) above-mentioned fibrillation fiber-filler compound is joined in slurry, in slurry, also can selectively add as required or not add untreated filler.Be that filler in final slurry is from the filler in fibrillation fiber-filler compound with supplement in addition the filler adding, or all from the filler in fibrillation fiber-filler compound, wherein the filler in fibrillation fiber-filler compound accounts for the 80%-100% of the filler gross mass in final slurry.
In described slurry, the consumption of filler is the 10%-300% of pulp fiber over dry quality, and wherein pulp fiber comprises the fibrillation fiber in fibrillation fiber-filler compound.
(4) in above-mentioned slurry, add starch, the addition of starch is the 1%-10% of slurry over dry quality.This starch can be anionic starch, oxidized starch, graft starch, amphoteric starch.
(5) diluted slurry then optionally adds or does not add reservation auxiliary agent in slurry, finally applies this slurry and carries out copy paper.Retaining auxiliary agent can select conventional binary or ternary to retain auxiliary agent, nano micro crystal cellulose (NCC) and (or) fibrillation cellulose (MFC) can be used as a kind of anion and retain auxiliary agent use, NCC and (or) MFC that preferably prepared by TEMPO catalytic oxidation.
A kind of slurry that contains above-mentioned fibrillation fiber-filler compound, filler in this slurry is from the filler in fibrillation fiber-filler compound and supplement in addition the filler of interpolation, or all from the filler in fibrillation fiber-filler compound, wherein the filler in fibrillation fiber-filler compound accounts for the 80%-100% of the filler gross mass in slurry.Preferably, the filler in slurry is all from the filler in fibrillation fiber-filler compound.
In described slurry, the consumption of filler is the 10%-300% of pulp fiber over dry quality, and wherein pulp fiber comprises the fibrillation fiber in fibrillation fiber-filler compound.
The paper that the slurry that application contains above-mentioned fibrillation fiber-filler compound makes, it contains above-mentioned fibrillation fiber-filler compound, and this paper has that higher ash content retention rate reaches 60%-95% and initial journey ash content retention rate reaches 55%-90%.Note: the ash content retention rate of general paper is 45%-90%, initial journey ash content retention rate is 40%-85%.
The paper that application said method makes, there is higher ash content retention rate, be that filler runs off less, concrete reason is: fibrillation fibrous material prepared by (1) TEMPO, and its comparison of ingredients is complicated, contains water-soluble and water-insoluble cellulose, water-insoluble cellulose is owing to having generated a large amount of carboxyls, between fiber, repulsion increases, and therefore at fibrous inside, causes layering, and tiny filler particles and (or) latex particle have an opportunity to enter fibrous inside; And water-soluble fibre or derivative are easily attached to paper making pulp and filling surface, different-grain diameter length, the composition of specification, when processing filler, has been brought into play synergy.(2) filler-fibrillation fiber-latex system, under the condition in temperature higher than latex vitrification point, processes, and its filler particles can be attached to fibrillation cellulose surface, distributes relatively even.And latex, under vitrified temperature conditions higher than latex, breakdown of emulsion occurs, a kind of possible mechanism is, filler, the fiber latex composition of vying each other, and latex composition is softening under higher temperature, makes filler particles set and fiber surface.(3) water-soluble cellulose in fibrillation cellulose aqueous slurry, understandable, and wherein a part is adsorbed by filling surface, can make the dispersiveness of filler be enhanced, and contributes to obtain equally distributed filler-cellulose composite.Within latter 4 hours of batching, filler particles is less or do not have in the precipitation of container bottom.(4) because filling surface has adsorbed part water-soluble cellulose, can predict, therefore filler particles surface has partially or completely been coated cellulose, therefore surface has had certain active function groups, in follow-up paper making process, can help to form stable chemical bonding between fiber and this compound.
Fibrillation fiber-filler compound of the present invention, by introducing latex that vitrification point is lower as the bonding agent between fibrillation fiber and filler, makes filler can be attached to equably fibrillation fiber surface.This fibrillation fiber-filler compound is made an addition in slurry, can effectively reduce the loss of filler, the paper that slurry is manufactured paper with pulp make has higher ash content retention rate.
Below by specific embodiment, the present invention is described further.
Comparative example 1
Get fibrillation cellulose, add the filler of 10 times of its fibrillation cellulose over dry quality, 600RPM stirs 5 minutes, concrete form please refer to the drawing 1, and the filler using is through homodisperse grinding calcium carbonate, it 95% distributes and is less than 2 microns with the particle diameter of improving quality.
Embodiment 1
The preparation of fibrillation fiber-filler compound, under concrete steps ginseng:
(a) get the aqueous slurry of 2g fibrillation fiber, be 1% solid the containing of described fibrillation fiber, opens agitating device.
(b) get 20g over dry filler, described filler is GCC, and it 95% is less than or equal to 2 microns with the particle average grain diameter of improving quality.
(c) filler is added in the aqueous slurry of fibrillation fibrous material, continue to add the styrene-butadiene latex with respect to packing quality 1wt%, its vitrification point is 10 ° of C.
(d) under 50 ° of C conditions, stir, constant temperature 5 minutes, makes fibrillation fiber-filler compound, concrete form please refer to the drawing 2.
Known from Fig. 1 and Fig. 2: Fig. 1, filler distributes to exist significantly at fibrillation fiber surface and reunites, and in Fig. 2, filler is evenly distributed at fibrillation fiber surface, without obviously reuniting.
The performance test results of embodiment 1 and comparative example 1 is as shown in following table one.
Table one
| Project | Comparative example 1 | Embodiment 1 |
| Filler particles surface evenness | 11.9 | 7.42 |
| Filler particles average-size | 4.5 micron | 3.9 micron |
Known according to the test result of table one: relative comparative example 1, in fibrillation fiber-filler compound of embodiment 1, filler sizes is more even.
Comparative example 2
Get 10g bleaching hardwood chemical pulp aqueous slurry, add the filler of relative slurry over dry quality 200%, continue to add the starch of relative slurry over dry quality 2%, dilution, handsheet, Substance 70gsm.
Embodiment 2
Fibrillation fiber-filler compound that embodiment 1 is made (containing 2g fibrillation fiber and 20g over dry filler), joining over dry quality is in bleaching hardwood chemical pulp (LBKP) aqueous slurry of 10g; Continue to add the starch of relative slurry over dry quality 2%, dilution, handsheet, Substance 70gsm.
The paper performance test result of embodiment 2 and comparative example 2 is as shown in following table two.
Table two
| Project | Comparative example 2 | Embodiment 2 |
| Basic weight g/m 2 | 72.3 | 73.1 |
| Thickness μ m | 94.7 | 85.7 |
| Bulk cc/g | 1.31 | 1.17 |
| Air permeability s | 10.5 | 33.5 |
| Folding time (1.0kg) | 3 | 4 |
| Burst index kPam 2/g | 0.84 | 0.99 |
| Tensile index Nm/g | 17.4 | 21.8 |
| Cohesive force kg.cm | 0.53 | 0.99 |
| Ash content % | 45.74 | 51.4 |
| Initial journey retention rate % | 42.1 | 63.3 |
| Ash content retention rate % | 68.7 | 82.2 |
Known according to the test result of table two: the relative paper of comparative example 2, the physical property of the paper of embodiment 2 promotes to some extent, and initial journey ash content retention rate and ash content retention rate all have significant lifting.
Comparative example 3
Get bleaching needle-point leaf pulp 50%, poplar hydrogen peroxide chemi-mechanical pulp APMP 50%, the aqueous slurry that amounts to 20g oven dry stock, be adjusted to slurry and dense being about under 4%, 600RPM stir 5 minutes, under stirring condition, adding quality is the moisture heavy calcium carbonate filling of oven dry stock quality 10%, continue to add the cationic starch of over dry slurry 0.4%, be diluted to slurry concentration approximately 0.3%, join the handsheet of folding arms, Substance is 70gsm.
Embodiment 3
Get over dry quality and be the aqueous carbonic acid calcium filler (be equivalent to 20g over dry slurry 10%) of 2g, the fibrillation fiber that adds packing quality 0.1%, continue to add the styrene-butadiene latex of filler weight 0.1%, its vitrification point is less than 10 ℃, under 50 ℃ of conditions, stir, be incubated 5 minutes, obtain a kind of fibrillation cellulose-filler compound.
Continue to get bleaching needle-point leaf pulp 50%, poplar hydrogen peroxide chemi-mechanical pulp (APMP) 50%, amounts to the aqueous slurry of 20g oven dry stock, is adjusted to that slurry is dense is about 4%, adds above-mentioned fibrillation cellulose-filler compound.Continue to add the starch of relative fiber over dry quality 0.4%, be diluted to slurry concentration approximately 0.3%, join the handsheet of folding arms, Substance is 70gsm.
Comparative example 4
Be with the difference of comparative example (3), amount of filler is 25% of pulp fiber over dry quality.All the other conditions are identical.
Embodiment 4
Get over dry quality and be the aqueous carbonic acid calcium filler (be equivalent to 20g over dry slurry 25%) of 5g, the fibrillation fiber that adds packing quality 0.1%, continue to add the styrene-butadiene latex of packing quality 0.1%, its vitrification point is less than 10 ℃, continues to add the borax of packing quality 0.1% as crosslinking agent.Under 50 ℃ of conditions, stir, be incubated 5 minutes, obtain a kind of fibrillation cellulose-filler compound.
Continue to get bleaching needle-point leaf pulp 50%, poplar hydrogen peroxide chemi-mechanical pulp (APMP) 50%, amounts to the aqueous slurry of 20g oven dry stock, is adjusted to that slurry is dense is about 4%, adds above-mentioned fibrillation cellulose-filler compound.Continue to add the starch of relative fiber over dry quality 0.4%, be diluted to slurry concentration approximately 0.3%, join the handsheet of folding arms, Substance is 70gsm.
The paper performance test result of embodiment 3-4 and comparative example 3-4 is as shown in following table three.
Table three
| Test event | Comparative example 3 | Embodiment 3 | Comparative example 4 | Embodiment 4 |
| Basic weight g/m 2 | 76.1 | 74.7 | 81.5 | 77.6 |
| Thickness μ m | 184.5 | 179.4 | 184.2 | 190.8 |
| Bulk cc/g | 2.42 | 2.40 | 2.26 | 2.46 |
| Air permeability s | 4.1 | 3.5 | 4.1 | 4.0 |
| Folding number (1.0kg) | 59 | 92 | 40 | 62 |
| Burst index kPam 2/g | 2.38 | 2.53 | 2.22 | 2.28 |
| Tensile index Nm/g | 43.8 | 46.1 | 40.0 | 42.1 |
| Cohesive force kg.cm | 0.97 | 1.02 | 0.85 | 0.92 |
| Ash content % | 3.86% | 5.49% | 9.94% | 12.54% |
| Initial journey ash content retains % | 40.1% | 58.1% | 55.2% | 71.7% |
| Ash content retention rate % | 42.5% | 60.4% | 59.6% | 75.2% |
Known according to the test result of table three: relative comparative example 3, the physical parameter of the paper of embodiment 3 is substantially approaching, but initial journey ash content retention rate and ash content retention rate all have significant lifting; Relative comparative example 4, the physical parameter of the paper of embodiment 4 is substantially approaching, but initial journey ash content retention rate and ash content retention rate all have significant lifting.
Comparative example 5
Get bleaching needle-point leaf pulp 50%, poplar hydrogen peroxide chemi-mechanical pulp (APMP) 30%, fibrillation cellulose 20%, the aqueous slurry that amounts to 20g oven dry stock, be adjusted to slurry and be densely about 4%, under 600RPM, stir 5 minutes, under stirring condition, adding over dry quality is the moisture heavy calcium carbonate filling of oven dry stock quality 300%, continue to add the cationic starch of over dry slurry 2%, be diluted with water to slurry dense 1%, add successively ternary to retain the cationic polyacrylamide of auxiliary agent 300PPM, the bentonite of 3600PPM, the anionic polyacrylamide of 800PPM, under 600RPM, stir 5 minutes, be diluted to slurry concentration approximately 0.3%, join the handsheet of folding arms, Substance is 100gsm.
Embodiment 5
Get over dry quality and be the aqueous carbonic acid calcium filler (be equivalent to 20g over dry slurry 300%) of 60g, add the fibrillation fiber (be equivalent to 20g over dry slurry 20%) of 4g.Continue to add the styrene-butadiene latex of packing quality 15%, its vitrification point is less than 10 ℃.Under 50 ℃ of conditions, stir, be incubated 5 minutes, obtain a kind of fibrillation cellulose-filler compound.
Continue to get bleaching needle-point leaf pulp 10g(be equivalent to 20g over dry slurry 50%), poplar hydrogen peroxide chemi-mechanical pulp (APMP) 6g(be equivalent to 20g over dry slurry 30%), account for 30% aqueous slurry of 20g bone dry fiber slurry, be adjusted to slurry and be densely about 4%, under 600RPM, stir 5 minutes, under stirring condition, add above-mentioned pretreated filler, continue to add the cationic starch of over dry slurry 2%, be diluted with water to slurry dense 1%, add successively ternary to retain the cationic polyacrylamide of each 300PPM of auxiliary agent, the bentonite of 3600PPM, the anionic polyacrylamide of 800PPM, under 600RPM, stir 5 minutes, be diluted to slurry concentration approximately 0.3%, join the handsheet of folding arms, Substance is 100gsm.
The paper performance test result of embodiment 5 and comparative example 5 is as shown in following table four.
Table four
| Test event | Comparative example 5 | Embodiment 5 |
| Basic weight g/m 2 | 107.9 | 112.0 |
| Thickness μ m | 134.9 | 72.0 |
| Bulk cc/g | 1.25 | 0.64 |
| Folding number 1kg | 2 | 11 |
| Air permeability s | 18.9 | 51.4 |
| Tensile index Nm/g | 7.2 | 16.6 |
| Cohesive force kg.cm | 0.64 | 2.25 |
| Ash content % | 59.6 | 62.4 |
| Initial journey ash content retains % | 49.2 | 84.0 |
| Ash content retention rate % | 79.5 | 95.5 |
Known according to the test result of table four: relative comparative example 5, initial journey ash content retention rate and the ash content retention rate of the paper of embodiment 5 all have significant lifting, and the physical property of paper, as folding number, tensile index, cohesive force all has lifting, and the dry linting that can effectively reduce paper falls a mao phenomenon.
In addition, those skilled in the art also can make various modifications, interpolation and the replacement in other form and details in the claims in the present invention scope of disclosure and spirit.Certainly, the variations such as various modifications, interpolation and replacement that these are made according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (24)
1. a fibrillation fiber-filler compound, it is characterized in that: this compound is mainly composited by fibrillation fibrous material, filler and latex, the 0.1%-10% that wherein in this compound, fibrillation fibrous material over dry quality is packing quality, latex quality is the 0.1%-15% of packing quality, and this latex is the latex that vitrification point is less than 20 ℃.
2. fibrillation fiber-filler compound as claimed in claim 1, it is characterized in that: this fibrillation fibrous material has elecrtonegativity, its surperficial carboxyl-content reaches 0.06-1.7mmol/g, and in fibrillation fibrous material, contain water-soluble fibre and water-insoluble fiber, wherein the over dry quality percentage composition of water-soluble fibre is 0.1%-50%, and the over dry quality percentage composition of water-insoluble fiber is 10%-99.9%.
3. fibrillation fiber-filler compound as claimed in claim 2, is characterized in that: water miscible cellulose includes nano micro crystal cellulose, nanometer fibrillation cellulose, compound sugar, fibrillation cellulose and derivative thereof.
4. fibrillation fiber-filler compound as claimed in claim 1, is characterized in that: this latex is that vitrification point is less than or equal to the latex of 10 ℃.
5. fibrillation fiber-filler compound as claimed in claim 1, is characterized in that: this latex is selected from polybutadiene latex, styrene-butadiene latex, carboxylic styrene butadiene latex, one or more of CATION styrene-butadiene latex, polyvinyl acetate Ruzhong.
6. fibrillation fiber-filler compound as claimed in claim 1, is characterized in that: the big or small uniformity that covers the filler particles on fibrillation fibrous material surface in this compound is less than 10.
7. fibrillation fiber-filler compound as claimed in claim 1, is characterized in that: in this filler, 50% is less than or equal to 2 microns with the packing material size of improving quality.
8. fibrillation fiber-filler compound as claimed in claim 1, it is characterized in that: in this fibrillation fiber-filler compound, also contain crosslinking agent, this crosslinking agent is borate, borax or twain-aldehyde compound crosslinking agent, the 0.1%-15% that the addition of this crosslinking agent is latex quality.
9. the preparation method of a fibrillation fiber-filler compound as described in any one in claim 1-8, it is characterized in that: the latex of the 0.1%-15% of the fibrillation cellulose of the 0.1%-20% of filler, packing quality and packing quality is mixed and made, and this latex is the latex that vitrification point is less than 20 ℃.
10. the preparation method of fibrillation fiber-filler compound as claimed in claim 9, is characterized in that: this latex is that vitrification point is less than or equal to the latex of 10 ℃.
The preparation method of 11. fibrillation fiber-filler compounds as claimed in claim 9, is characterized in that: the temperature of controlling mixed liquor in preparation process is 20-110 ℃.
12. 1 kinds of slurries, it is characterized in that: this slurry contains fibrillation fiber-filler compound, this compound is mainly composited by fibrillation fibrous material, filler and latex, the 0.1%-10% that in this compound, fibrillation fibrous material over dry quality is packing quality, latex quality is the 0.1%-15% of packing quality, and this latex is the latex that vitrification point is less than 20 ℃.
13. slurries as claimed in claim 12, it is characterized in that: this fibrillation fibrous material has elecrtonegativity, its surperficial carboxyl-content reaches 0.06-1.7mmol/g, and in fibrillation fibrous material, contain water-soluble fibre and water-insoluble fiber, wherein the over dry quality percentage composition of water-soluble fibre is 0.1%-50%, and the over dry quality percentage composition of water-insoluble fiber is 10%-99.9%.
14. slurries as claimed in claim 13, is characterized in that: water miscible cellulose includes nano micro crystal cellulose, nanometer fibrillation cellulose, compound sugar, fibrillation cellulose and derivative thereof.
15. slurries as claimed in claim 12, is characterized in that: this latex is that vitrification point is less than or equal to the latex of 10 ℃.
16. slurries as claimed in claim 12, is characterized in that: this latex is selected from polybutadiene latex, styrene-butadiene latex, carboxylic styrene butadiene latex, one or more of CATION styrene-butadiene latex, polyvinyl acetate Ruzhong.
17. slurries as claimed in claim 12, it is characterized in that: the filler in this slurry is from the filler in fibrillation fiber-filler compound and supplement in addition the filler of interpolation, or all from the filler in fibrillation fiber-filler compound, wherein the filler in fibrillation fiber-filler compound accounts for the 80%-100% of the filler gross mass in final slurry.
18. slurries as claimed in claim 12, is characterized in that: the big or small uniformity that covers the filler particles on fibrillation fibrous material surface in this compound is less than 10.
19. slurries as claimed in claim 12, is characterized in that: in this filler, 50% is less than or equal to 2 microns with the packing material size of improving quality.
20. slurries as claimed in claim 12, is characterized in that: in described slurry, the consumption of filler is the 10%-300% of pulp fiber over dry quality, and wherein pulp fiber comprises the fibrillation fiber in fibrillation fiber-filler compound.
21. slurries as claimed in claim 12, is characterized in that: in this slurry, be also added with starch, retain auxiliary agent.
22. slurries as claimed in claim 12, is characterized in that: in this fibrillation fiber-filler compound, also contain crosslinking agent, this crosslinking agent is borate, borax or twain-aldehyde compound crosslinking agent, the 0.1%-15% that the addition of this crosslinking agent is latex quality.
23. 1 kinds of application rights require the paper that in 12-22, described in any one, slurry is manufactured paper with pulp and made, and contain fibrillation fibrous material, filler, latex in this paper.
24. paper as claimed in claim 23, is characterized in that: the ash content retention rate of this paper reaches 60%-95%, and initial journey ash content retention rate reaches 55%-90%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310045150.XA CN103966889B (en) | 2013-02-05 | 2013-02-05 | Compound and preparation method thereof, applies its slurry and paper |
| US14/104,068 US20140216672A1 (en) | 2013-02-05 | 2013-12-12 | Modified filler composition and papermaking process using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310045150.XA CN103966889B (en) | 2013-02-05 | 2013-02-05 | Compound and preparation method thereof, applies its slurry and paper |
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| Publication Number | Publication Date |
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| CN103966889A true CN103966889A (en) | 2014-08-06 |
| CN103966889B CN103966889B (en) | 2016-03-09 |
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| CN201310045150.XA Active CN103966889B (en) | 2013-02-05 | 2013-02-05 | Compound and preparation method thereof, applies its slurry and paper |
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| Country | Link |
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| US (1) | US20140216672A1 (en) |
| CN (1) | CN103966889B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104452425A (en) * | 2014-11-06 | 2015-03-25 | 陕西科技大学 | Microfiber cellulose enveloped and retained high filling papermaking process |
| CN112593439A (en) * | 2016-02-25 | 2021-04-02 | 国际纸业公司 | Crosslinked kraft pulp compositions and methods |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102233086B1 (en) * | 2012-05-15 | 2021-03-29 | 만트로즈-호이저 컴패니, 인코포레이티드 | Seaweed-based food packaging coating |
| KR102358824B1 (en) * | 2014-01-29 | 2022-02-07 | 이섬 리서치 디벨러프먼트 컴파니 오브 더 히브루 유니버시티 오브 예루살렘 엘티디. | Porous nanocrystalline cellulose structures |
| RU2753445C2 (en) * | 2016-09-16 | 2021-08-16 | Соленис Текнолоджиз, Л.П. | Improved dehydration efficiency in paper-making systems using micro-fibrillated cellulose |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106213A (en) * | 1986-09-09 | 1988-03-23 | 纳幕尔杜邦公司 | Fill composition and the application in wood fiber paper is made thereof |
| US20120080156A1 (en) * | 2010-10-01 | 2012-04-05 | Fpinnovations | Cellulose-reinforced high mineral content products and methods of making the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6749721B2 (en) * | 2000-12-22 | 2004-06-15 | Kimberly-Clark Worldwide, Inc. | Process for incorporating poorly substantive paper modifying agents into a paper sheet via wet end addition |
| GB0908401D0 (en) * | 2009-05-15 | 2009-06-24 | Imerys Minerals Ltd | Paper filler composition |
| SE536744C2 (en) * | 2010-05-12 | 2014-07-08 | Stora Enso Oyj | A process for manufacturing a composition containing fibrillated cellulose and a composition |
| SE536746C2 (en) * | 2010-05-12 | 2014-07-08 | Stora Enso Oyj | A composition containing microfibrillated cellulose and a process for making a composition |
| KR20140129032A (en) * | 2012-02-24 | 2014-11-06 | 허큘레스 인코포레이티드 | Nanocrystalline cellulose (ncc) in tape joint compound (jc) |
| EP2653508A1 (en) * | 2012-04-19 | 2013-10-23 | Imerys S.A. | Compositions for paint |
-
2013
- 2013-02-05 CN CN201310045150.XA patent/CN103966889B/en active Active
- 2013-12-12 US US14/104,068 patent/US20140216672A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106213A (en) * | 1986-09-09 | 1988-03-23 | 纳幕尔杜邦公司 | Fill composition and the application in wood fiber paper is made thereof |
| US20120080156A1 (en) * | 2010-10-01 | 2012-04-05 | Fpinnovations | Cellulose-reinforced high mineral content products and methods of making the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104452425A (en) * | 2014-11-06 | 2015-03-25 | 陕西科技大学 | Microfiber cellulose enveloped and retained high filling papermaking process |
| CN112593439A (en) * | 2016-02-25 | 2021-04-02 | 国际纸业公司 | Crosslinked kraft pulp compositions and methods |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103966889B (en) | 2016-03-09 |
| US20140216672A1 (en) | 2014-08-07 |
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